Substituted benzo[4,5]imidazo[1,2-F]phenanthridines, dibenzo[I.K]benzo[4,5]imidazo[1,2-F]benzofurophenanthridines and dibenzo[I.K]benzo[4,5]imidazo[1,2-F]benzo[4,5]thienophenanthridines as thermally assisted delayed fluorescent materials

ABSTRACT

Thermally assisted delayed fluorescent materials with triad-type materials for use in full color displays and lighting applications with the following generic structures are provided:

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a continuation of U.S. patent applicationSer. No. 15/984,102, filed May 18, 2018, now allowed, which claims thebenefit of U.S. Patent Application No. 62/508,555, filed on May 19,2017, all of which applications are incorporated herein by reference intheir entireties.

STATEMENT OF GOVERNMENT INTEREST

This invention was made with government support under DE-EE0007090awarded by the Department of Energy. The government has certain rightsin the invention.

TECHNICAL FIELD

This invention relates to thermally assisted delayed fluorescentmaterials with triad-type materials for use in full color displays andlighting applications.

BACKGROUND

Most thermally assisted delayed fluorescent (TADF) material designs relyon the donor-acceptor concept, which requires a strong donor and astrong acceptor group with large molecular geometry distortion to lowerthe highest occupied molecular orbital (HOMO)-lowest unoccupiedmolecular orbital (LUMO) energy gap and minimize the energy splittingbetween the lowest singlet excited state (S1) and the lowest tripletexcited state (T1). Such design tends to use an acceptor type group withless electrochemical stability, resulting in decreased deviceoperational stability.

SUMMARY

Light emitting complexes represented by the following General Formulasare described.

Implementations include a light emitting diode including a lightemitting complex represented by one of the General Formulas above, aswell as a light emitting device including the light emitting diode.

These general and specific aspects may be implemented using a device,system or method, or any combination of devices, systems, or methods.The details of one or more embodiments are set forth in the accompanyingdrawings and the description below. Other features, objects, andadvantages will be apparent from the description and drawings, and fromthe claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts emission mechanisms of organic emitters.

FIGS. 2A-2E depict donor-acceptor (D-A) type, non-cyclicdonor-acceptor-donor′ (D-A-D′) type, non-cyclic acceptor-donor-acceptor′(A-D-A′) type, cyclic donor-acceptor-donor′ (D-A-D′) type, and cyclicacceptor-donor-acceptor′ (A-D-A′) type TADF materials, respectively.

FIGS. 3A and 3B depict proposed emission mechanisms for cyclic D-A-D′type and cyclic A-D-A′ type TADF materials, respectively.

FIG. 4 depicts an organic light emitting diode (OLED).

FIGS. 5A-5C show external quantum efficiency (EQE) vs. luminance, EQEvs. current density, and an electroluminescence (EL) spectrum,respectively, of DFE-3 with the device structure described in Example 3.FIG. 5D shows device operational lifetime for the device.

DETAILED DESCRIPTION

Emission mechanisms inside of device settings for organic emissivematerials include fluorescence, phosphorescence, thermally assisteddelayed fluorescence (TADF) and metal-assisted delayed fluorescence(MADF), as illustrated in FIG. 1. The latter three have the potential toharvest 100% electro-generated excitons. TADF designs described hereininclude triad-type materials, such as cyclic donor-donor′-acceptor(D-D′-A) or cyclic donor-acceptor-acceptor′ (D-A-A′) materials depictedin FIG. 1, with a possible pair of conjugated donor-type (oracceptor-type) functional groups that are also individually conjugatedwith the corresponding acceptor-type (or donor-type) functional groupthrough covalent bonding. Thus, the singlet excited state energy will besignificantly reduced due to the conjugation of D-D′-A (or D-A-A′) whilethe triplet will still prefer to localize on one of D-A pairs andmaintain the similar triplet state energy, leading to a smallsinglet-triplet energy splitting. Such a design allows the incorporationof weak donors or acceptors, making TADF material more feasible asstable emitters or host materials for organic light emitting diode(OLED) applications.

FIGS. 2A-2E depict D-A type, non-cyclic D-A-D′ type, non-cyclic A-D-A′type, cyclic D-A-D′ type, and cyclic A-D-A′ type TADF materials,respectively. FIGS. 3A and 3B depict proposed emission mechanisms forcyclic D-A-D′ type and cyclic A-D-A′ type TADF materials, respectively.

Examples of donor groups are shown below.

in which:

X¹ represents O, NR¹, S, or PR¹,

X² represents O, NR¹, S, CR¹R², SiR¹R², C═O, GeR¹R², PR¹, R¹P═O, As R¹,R¹As═O, S═O, SO₂, Se═O, SeO₂, BR¹, AlR¹, R¹Bi═O, BiR¹, or

each of R¹, R², R³, and R⁴ is independently absent or present as asingle substituent or multiple substituents, valency permitting, andeach R¹, R², R³, and R⁴ present independently represents deuterium,halogen, hydroxyl, thiol, nitro, cyanide, isocyanide, sulfinyl,mercapto, sulfa, carboxyl, hydrazino; substituted or unsubstituted:aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl,alkenyl, alkenyl, amino, monoalkylamino, dialkylamino, monoarylamino,diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl,acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino,sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl,polymeric; or any conjugate or combination thereof.

In some implementations, each —R¹, —R², —R³, and —R⁴ independentlyrepresents one of the following moieties.

where R and each R⁷ present, valency permitting, independentlyrepresents deuterium, halogen, hydroxyl, thiol, nitro, cyano, cyanide,isocyanide, sulfinyl, mercapto, sulfa, carboxyl, hydrazino; substitutedor unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl,heteroaryl, alkyl, alkenyl, alkenyl, amino, monoalkylamino,dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl,aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino,aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio,ureido, phosphoramide, silyl, polymeric; or any conjugate or combinationthereof.

Examples of acceptor groups are shown below.

in which:

X¹ represents O, NR¹, S, or PR¹.

X² represents O, NR¹, S, CR¹R², SiR¹R², C═O, GeR¹R², PR¹, R¹P═O, As R¹,R¹As═O, S═O, SO₂, Se═O, SeO₂, BR¹, AlR¹, R¹Bi═O, BiR¹,

each of R¹, R², R³, and R⁴ is independently absent or present as asingle substituent or multiple substituents, valency permitting, andeach R¹, R², R³, and R⁴ present independently represents deuterium,halogen, hydroxyl, thiol, nitro, cyanide, isocyanide, sulfinyl,mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted:cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl,alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino,diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl,acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino,sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl,polymeric; or any conjugate or combination thereof.

In some implementations, —R¹, —R², —R³, and —R⁴ may independentlyrepresent one of the following moieties, where R and R⁷ are definedherein.

The following General Formulas represent cyclic D-A-D′ and A-D-A′ TADFmaterials.

Examples of

are shown below.

Examples of

are shown below.

Examples of

are shown below.

Examples of

are shown below.

In the examples:

N is nitrogen;

X¹ represents O, NR¹, S, or PR¹,

X² represents O, NR¹, S, CR¹R², SiR¹R², C═O, GeR¹R², PR¹, R¹P═O, As R¹,R¹As═O, S═O, SO₂, Se═O, SeO₂, BR¹, AlR¹, R¹Bi═O, or BiR¹, or

represents one of

each of R¹, R², R³, and R⁴ is independently absent or present as asingle substituent or multiple substituents, valency permitting, andeach R¹, R², R³, and R⁴ present independently represents deuterium,halogen, hydroxyl, thiol, nitro, cyanide, isocyanide, sulfinyl,mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted:aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl,alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino,diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl,acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino,sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl,polymeric; or any conjugate or combination thereof.

In some implementations, one or more of —R¹, —R², —R³, and —R⁴ eachindependently represents one of the following moieties, where R and R⁷are defined herein.

Examples of cyclic, D-A-D′ and A-D-A′ TADF materials are shown below.

As referred to herein, a linking atom or group connects two atoms suchas, for example, an N atom and a C atom. A linking atom or group is inone aspect disclosed as L¹, L², L³, etc. herein. The linking atom canoptionally, if valency permits, have other chemical moieties attached.For example, in one aspect, an oxygen would not have any other chemicalgroups attached as the valency is satisfied once it is bonded to twogroups (e.g., N and/or C groups). In another aspect, when carbon is thelinking atom, two additional chemical moieties can be attached to thecarbon. Suitable chemical moieties include amine, amide, thiol, aryl,heteroaryl, cycloalkyl, and heterocyclyl moieties. The term “cyclicstructure” or the like terms used herein refer to any cyclic chemicalstructure which includes, but is not limited to, aryl, heteroaryl,cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocycliccarbene.

As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, and aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,for example, those described below. The permissible substituents can beone or more and the same or different for appropriate organic compounds.For purposes of this disclosure, the heteroatoms, such as nitrogen, canhave hydrogen substituents and/or any permissible substituents oforganic compounds described herein which satisfy the valences of theheteroatoms. This disclosure is not intended to be limited in any mannerby the permissible substituents of organic compounds. Also, the terms“substitution” or “substituted with” include the implicit proviso thatsuch substitution is in accordance with permitted valence of thesubstituted atom and the substituent, and that the substitution resultsin a stable compound, e.g., a compound that does not spontaneouslyundergo transformation such as by rearrangement, cyclization,elimination, etc. It is also contemplated that, in certain aspects,unless expressly indicated to the contrary, individual substituents canbe further optionally substituted (i.e., further substituted orunsubstituted).

In defining various terms, “A¹”, “A²”, “A³”, “A⁴” and “A⁵” are usedherein as generic symbols to represent various specific substituents.These symbols can be any substituent, not limited to those disclosedherein, and when they are defined to be certain substituents in oneinstance, they can, in another instance, be defined as some othersubstituents.

The term “alkyl” as used herein is a branched or unbranched saturatedhydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl,isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkylgroup can be cyclic or acyclic. The alkyl group can be branched orunbranched. The alkyl group can also be substituted or unsubstituted.For example, the alkyl group can be substituted with one or more groupsincluding, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether,halide, hydroxy, nitro, silyl, sulfa-oxo, or thiol, as described herein.A “lower alkyl” group is an alkyl group containing from one to six(e.g., from one to four) carbon atoms.

Throughout the specification “alkyl” is generally used to refer to bothunsubstituted alkyl groups and substituted alkyl groups; however,substituted alkyl groups are also specifically referred to herein byidentifying the specific substituent(s) on the alkyl group. For example,the term “halogenated alkyl” or “haloalkyl” specifically refers to analkyl group that is substituted with one or more halide, e.g., fluorine,chlorine, bromine, or iodine. The term “alkoxyalkyl” specifically refersto an alkyl group that is substituted with one or more alkoxy groups, asdescribed below. The term “alkylamino” specifically refers to an alkylgroup that is substituted with one or more amino groups, as describedbelow, and the like. When “alkyl” is used in one instance and a specificterm such as “alkylalcohol” is used in another, it is not meant to implythat the term “alkyl” does not also refer to specific terms such as“alkylalcohol” and the like.

This practice is also used for other groups described herein. That is,while a term such as “cycloalkyl” refers to both unsubstituted andsubstituted cycloalkyl moieties, the substituted moieties can, inaddition, be specifically identified herein; for example, a particularsubstituted cycloalkyl can be referred to as, e.g., an“alkylcycloalkyl.” Similarly, a substituted alkoxy can be specificallyreferred to as, e.g., a “halogenated alkoxy.” a particular substitutedalkenyl can be, e.g., an “alkenylalcohol,” and the like. Again, thepractice of using a general term, such as “cycloalkyl,” and a specificterm, such as “alkylcycloalkyl,” is not meant to imply that the generalterm does not also include the specific term.

The term “cycloalkyl” as used herein is a non-aromatic carbon-based ringcomposed of at least three carbon atoms. Examples of cycloalkyl groupsinclude, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, norbornyl, and the like. The term “heterocycloalkyl” is atype of cycloalkyl group as defined above, and is included within themeaning of the term “cycloalkyl,” where at least one of the carbon atomsof the ring is replaced with a heteroatom such as, but not limited to,nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl group andheterocycloalkyl group can be substituted or unsubstituted. Thecycloalkyl group and heterocycloalkyl group can be substituted with oneor more groups including, but not limited to, alkyl, cycloalkyl, alkoxy,amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol asdescribed herein.

The terms “alkoxy” and “alkoxyl” as used herein to refer to an alkyl orcycloalkyl group bonded through an ether linkage; that is, an “alkoxy”group can be defined as -OA¹ where A¹ is alkyl or cycloalkyl as definedabove. “Alkoxy” also includes polymers of alkoxy groups as justdescribed; that is, an alkoxy can be a polyether such as -OA¹-OA² or-OA¹-(OA²)_(a)-OA³, where “a” is an integer of from 1 to 200 and A¹, A²,and A³ are alkyl and/or cycloalkyl groups.

The term “alkenyl” as used herein is a hydrocarbon group of from 2 to 24carbon atoms with a structural formula containing at least onecarbon-carbon double bond. Asymmetric structures such as (A¹A²)C═C(A³A⁴)are intended to include both the F and Z isomers. This can be presumedin structural formulae herein wherein an asymmetric alkene is present,or it can be explicitly indicated by the bond symbol C═C. The alkenylgroup can be substituted with one or more groups including, but notlimited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl,cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, orthiol, as described herein.

The term “cycloalkenyl” as used herein is a non-aromatic carbon-basedring composed of at least three carbon atoms and containing at least onecarbon-carbon double bound, i.e., C═C. Examples of cycloalkenyl groupsinclude, but are not limited to, cyclopropenyl, cyclobutenyl,cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl,norbornenyl, and the like. The term “heterocycloalkenyl” is a type ofcycloalkenyl group as defined above, and is included within the meaningof the term “cycloalkenyl,” where at least one of the carbon atoms ofthe ring is replaced with a heteroatom such as, but not limited to,nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl group andheterocycloalkenyl group can be substituted or unsubstituted. Thecycloalkenyl group and heterocycloalkenyl group can be substituted withone or more groups including, but not limited to, alkyl, cycloalkyl,alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl,aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone,azide, nitro, silyl, sulfo-oxo, or thiol as described herein.

The term “alkynyl” as used herein is a hydrocarbon group of 2 to 24carbon atoms with a structural formula containing at least onecarbon-carbon triple bond. The alkynyl group can be unsubstituted orsubstituted with one or more groups including, but not limited to,alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl,aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether,halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, asdescribed herein.

The term “cycloalkynyl” as used herein is a non-aromatic carbon-basedring composed of at least seven carbon atoms and containing at least onecarbon-carbon triple bound. Examples of cycloalkynyl groups include, butare not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and thelike. The term “heterocycloalkynyl” is a type of cycloalkenyl group asdefined above, and is included within the meaning of the term“cycloalkynyl,” where at least one of the carbon atoms of the ring isreplaced with a heteroatom such as, but not limited to, nitrogen,oxygen, sulfur, or phosphorus. The cycloalkynyl group andheterocycloalkynyl group can be substituted or unsubstituted. Thecycloalkynyl group and heterocycloalkynyl group can be substituted withone or more groups including, but not limited to, alkyl, cycloalkyl,alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl,aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone,azide, nitro, silyl, sulfo-oxo, or thiol as described herein.

The term “aryl” as used herein is a group that contains any carbon-basedaromatic group including, but not limited to, benzene, naphthalene,phenyl, biphenyl, phenoxybenzene, and the like. The term “aryl” alsoincludes “heteroaryl,” which is defined as a group that contains anaromatic group that has at least one heteroatom incorporated within thering of the aromatic group. Examples of heteroatoms include, but are notlimited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term“non-heteroaryl,” which is also included in the term “aryl,” defines agroup that contains an aromatic group that does not contain aheteroatom. The aryl group can be substituted or unsubstituted. The arylgroup can be substituted with one or more groups including, but notlimited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl,cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiolas described herein. The term “biaryl” is a specific type of aryl groupand is included in the definition of “aryl.” Biaryl refers to two arylgroups that are bound together via a fused ring structure, as innaphthalene, or are attached via one or more carbon-carbon bonds, as inbiphenyl.

The term “aldehyde” as used herein is represented by the formula —C(O)H.Throughout this specification “C(O)” is a short hand notation for acarbonyl group, i.e., C═O.

The terms “amine” or “amino” as used herein are represented by theformula —NA¹A², where A¹ and A² can be, independently, hydrogen oralkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl,or heteroaryl group as described herein.

The term “alkylamino” as used herein is represented by the formula—NH(-alkyl) where alkyl is a described herein. Representative examplesinclude, but are not limited to, methylamino group, ethylamino group,propylamino group, isopropylamino group, butylamino group, isobutylaminogroup, (sec-butyl)amino group, (tert-butyl)amino group, pentylaminogroup, isopentylamino group, (tert-pentyl)amino group, hexylamino group,and the like.

The term “dialkylamino” as used herein is represented by the formula—N(-alkyl)₂ where alkyl is a described herein. Representative examplesinclude, but are not limited to, dimethylamino group, diethyl aminogroup, dipropylamino group, diisopropylamino group, dibutylamino group,diisobutylamino group, di(sec-butyl)amino group, di(tert-butyl)aminogroup, dipentylamino group, diisopentylamino group, di(tert-pentyl)aminogroup, dihexylamino group, N-ethyl-N-methylamino group,N-methyl-N-propylamino group, N-ethyl-N-propylamino group and the like.

The term “carboxylic acid” as used herein is represented by the formula—C(O)OH.

The term “ester” as used herein is represented by the formula —OC(O)A¹or —C(O)OA¹; where A¹ can be alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.The term “polyester” as used herein is represented by the formula-(A¹O(O)C-A²-C(O)O)_(a)— or -(A¹O(O)C-A²-OC(O))_(a)—, where A¹ and A²can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and“a” is an integer from 1 to 500. “Polyester” is as the term used todescribe a group that is produced by the reaction between a compoundhaving at least two carboxylic acid groups with a compound having atleast two hydroxyl groups.

The term “ether” as used herein is represented by the formula A¹OA²,where A¹ and A² can be, independently, an alkyl, cycloalkyl, alkenyl,cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group describedherein. The term “polyether” as used herein is represented by theformula -(A¹O-A²O)_(a)—, where A¹ and A² can be, independently, analkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl,or heteroaryl group described herein and “a” is an integer of from 1 to500. Examples of polyether groups include polyethylene oxide,polypropylene oxide, and polybutylene oxide.

The term “halide” or “halo” as used herein refers to the halogensfluorine, chlorine, bromine, and iodine.

The term “heterocyclyl,” as used herein refers to single andmulti-cyclic non-aromatic ring systems and “heteroaryl as used hereinrefers to single and multi-cyclic aromatic ring systems: in which atleast one of the ring members is other than carbon. The terms includesazetidine, dioxane, furan, imidazole, isothiazole, isoxazole,morpholine, oxazole, oxazole, including, 1,2,3-oxadiazole,1,2,5-oxadiazole and 1,3,4-oxadiazole, piperazine, piperidine, pyrazine,pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine,tetrahydrofuran, tetrahydropyran, tetrazine, including1,2,4,5-tetrazine, tetrazole, including 1,2,3,4-tetrazole and1,2,4,5-tetrazole, thiadiazole, including, 1,2,3-thiadiazole,1,2,5-thiadiazole, and 1,3,4-thiadiazole, thiazole, thiophene, triazine,including 1,3,5-triazine and 1,2,4-triazine, triazole, including,1,2,3-triazole, 1,3,4-triazole, and the like.

The term “hydroxyl” as used herein is represented by the formula —OH.

The term “ketone” as used herein is represented by the formula A¹C(O)A²,where A¹ and A² can be, independently, an alkyl, cycloalkyl, alkenyl,cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group asdescribed herein.

The term “azide” as used herein is represented by the formula —N₃.

The term “nitro” as used herein is represented by the formula —NO₂.

The term “cyanide” as used herein is represented by the formula —CN.

The term “silyl” as used herein is represented by the formula —SiA¹A²A³,where A¹, A², and A³ can be, independently, hydrogen or an alkyl,cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl,or heteroaryl group as described herein.

The term “sulfa-oxo” as used herein is represented by the formulas—S(O)A¹, —S(O)₂A¹, —OS(O)₂A¹, or —OS(O)₂OA¹, where A¹ can be hydrogen oran alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl,aryl, or heteroaryl group as described herein. Throughout thisspecification “S(O)” is a short hand notation for S═O. The term“sulfonyl” is used herein to refer to the sulfo-oxo group represented bythe formula —S(O)₂A¹, where A¹ can be hydrogen or an alkyl, cycloalkyl,alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl groupas described herein. The term “sulfone” as used herein is represented bythe formula A¹S(O)₂A², where A¹ and A² can be, independently, an alkyl,cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, orheteroaryl group as described herein. The term “sulfoxide” as usedherein is represented by the formula A¹S(O)A², where A¹ and A² can be,independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,cycloalkynyl, aryl, or heteroaryl group as described herein.

The term “thiol” as used herein is represented by the formula —SH.

“R,” “R¹,” “R²,” “R³,” “R^(n),” where n is an integer, as used hereincan, independently, possess one or more of the groups listed above. Forexample, if R¹ is a straight chain alkyl group, one of the hydrogenatoms of the alkyl group can optionally be substituted with a hydroxylgroup, an alkoxy group, an alkyl group, a halide, and the like.Depending upon the groups that are selected, a first group can beincorporated within second group or, alternatively, the first group canbe pendant (i.e., attached) to the second group. For example, with thephrase “an alkyl group comprising an amino group,” the amino group canbe incorporated within the backbone of the alkyl group. Alternatively,the amino group can be attached to the backbone of the alkyl group. Thenature of the group(s) that is (are) selected will determine if thefirst group is embedded or attached to the second group.

Compounds described herein may contain “optionally substituted”moieties. In general, the term “substituted,” whether preceded by theterm “optionally” or not, means that one or more hydrogens of thedesignated moiety are replaced with a suitable substituent. Unlessotherwise indicated, an “optionally substituted” group may have asuitable substituent at each substitutable position of the group, andwhen more than one position in any given structure may be substitutedwith more than one substituent selected from a specified group, thesubstituent may be either the same or different at every position.Combinations of substituents envisioned by this disclosure arepreferably those that result in the formation of stable or chemicallyfeasible compounds. In is also contemplated that, in certain aspects,unless expressly indicated to the contrary, individual substituents canbe further optionally substituted (i.e., further substituted orunsubstituted).

In some aspects, a structure of a compound can be represented by aformula:

which is understood to be equivalent to a formula:

wherein n is typically an integer. That is, R^(n) is understood torepresent five independent substituents, R^(n(a)), R^(n(b)), R^(n(c)),R^(n(d)), R^(n(e)). By “independent substituents,” it is meant that eachR substituent can be independently defined. For example, if in oneinstance R^(n(a)) is halogen, then R^(n(b)) is not necessarily halogenin that instance. In a case where there is a single R^(n) (e.g., onlyR^(n(a))), R^(n) is referred to as a “single substituent.” In a casewhere there are two or more R^(n) (e.g., at least R^(n(a)) and R^(n(b)))R^(n) is referred to as a “multiple substituents.”

Several references to R, R¹, R², R³, R⁴, R⁵, R⁶, etc. are made inchemical structures and moieties disclosed and described herein. Anydescription of R, R¹, R², R³, R⁴, R⁵, R⁶, etc. in the specification isapplicable to any structure or moiety reciting R, R¹, R², R³, R⁴, R⁵,R⁶, etc. respectively.

The compounds disclosed herein are suited for use in a wide variety ofdevices, including, for example, organic light emitting diodes (OLEDs)for full color displays and lighting applications.

Also disclosed herein are compositions including one or more compoundsdisclosed herein. The present disclosure provides light emitting devicesthat include one or more compositions described herein. The presentdisclosure also provides a photovoltaic device comprising one or morecomplexes or compositions described herein. Further, the presentdisclosure also provides a luminescent display device comprising one ormore compounds described herein.

Compounds described herein can be used in a light emitting device suchas an OLED. FIG. 4 depicts a cross-sectional view of an OLED 100. OLED100 includes substrate 102, anode 104, hole-transporting material(s)(HTL) 106, light processing material 108, electron-transportingmaterial(s) (ETL) 110, and a metal cathode layer 112. Anode 104 istypically a transparent material, such as indium tin oxide. Lightprocessing material 108 may be an emissive material (EML) including anemitter and a host.

In various aspects, any of the one or more layers depicted in FIG. 1 mayinclude indium tin oxide (ITO), poly(3,4-ethylenedioxythiophene)(PEDOT), polystyrene sulfonate (PSS),N,N′-di-1-naphthyl-N,N-diphenyl-1,1′-biphenyl-4,4′diamine (NPD),1,1-bis((di-4-tolylamino)phenyl)cyclohexane (TAPC),2,6-Bis(N-carbazolyl)pyridine (mCpy),2,8-bis(diphenylphosphoryl)dibenzothiophene (PO15), LiF, Al, or acombination thereof.

Light processing material 108 may include one or more compounds of thepresent disclosure optionally together with a host material. The hostmaterial can be any suitable host material known in the art. Theemission color of an OLED is determined by the emission energy (opticalenergy gap) of the light processing material 108, which can be tuned bytuning the electronic structure of the emitting compounds, the hostmaterial, or both. Both the hole-transporting material in the HTL layer106 and the electron-transporting material(s) in the ETL layer 110 mayinclude any suitable hole-transporter known in the art.

EXAMPLES

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how thecompounds, compositions, articles, devices and/or methods claimed hereinare made and evaluated, and are intended to be purely exemplary and arenot intended to be limiting in scope. Some of these synthetic exampleshave been performed. Others are based on an understanding of relatedsynthetic procedures and are predictive in nature. Efforts have beenmade to ensure accuracy with respect to numbers (e.g., amounts,temperature, etc.), but some errors and deviations should be accountedfor. Unless indicated otherwise, parts are parts by weight, temperatureis in ° C. or is at ambient temperature, and pressure is at or nearatmospheric.

Various methods for the preparation method of the compounds describedherein are recited in the examples. These methods are provided toillustrate various methods of preparation, but are not intended to limitany of the methods recited herein. Accordingly, one of skill in the artin possession of this disclosure could readily modify a recited methodor utilize a different method to prepare one or more of the compoundsdescribed herein. The following aspects are only exemplary and are notintended to be limiting in scope. Temperatures, catalysts,concentrations, reactant compositions, and other process conditions canvary, and one of skill in the art, in possession of this disclosure,could readily select appropriate reactants and conditions for a desiredcomplex.

An ortho-phenylenediamine (1.0 mmol; 1.0 equiv) and an aldehyde (1.0mmol; 1.0 equiv) were dissolved in wet DMF (DMF 9.0 mL, H₂O 1.0 mL). Theresulting reaction mixture was stirred at 80° C. in an open flask, andthe reaction progress was monitored by TLC. On the complete consumptionof aldehyde, the reaction mixture was cooled to room temperature andconcentrated under reduced pressure. The crude product obtained waspurified by column chromatography on silica gel to afford thecorresponding product.

A flame-dried Schlenk tube with a magnetic stir bar was charged withPd(PPh₃)₄ (28.8 mg, 25.0 μmol, 10 mol %), Xantphos (14.6 mg, 25.0 μmol,10 mol %), Cs₂CO₃ (243 mg, 0.75 mmol) and 2-aryl-N-heteroarenes (0.30mmol, 1.2 equiv.). Then. 1,2-dihaloarenes (0.25 mmol) and DMF (2.0 mL)were added to the reaction mixture under an N₂ atmosphere. The reactionmixture was stirred for 10 min at room temperature, and then heated at140° C. in a pre-heated oil bath for 24 h. After that, the reactionmixture was cooled to room temperature, diluted with CH₂Cl₂ (10 mL),filtered through a Celite pad, and washed with CH₂Cl₂ (10-20 mL). Thecombined organic extracts were concentrated and the resulting residuewas purified by column chromatography on silica gel to provide thedesired product.

Example 1

Synthesis of DFE-1

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-bromo-3-chloropyridine (1.2 eq). Then, BImPhen(1 eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-1 in 23% yield.

Example 2

Synthesis of DFE-2

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2,3-dichloropyrazine (1.2 eq). Then, BImPhen (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-2 in 34% yield.

Example 3

Synthesis of DFE-3

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and -chloro-3-iodopyridine (1.2 eq). Then, BImPhen (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-3 in 29% yield.

FIGS. 5A-5C show a plot of external quantum efficiency (EQE) vs.luminance, a plot of EQE vs. current density, and an EL spectrum ofDFE-3 with device structure: ITO (40 nm)/HATCN (10 nm)/NPD (40nm)/BisPCz (10 nm)/6% PyPID:mCBP (25 nm)/mCBT (10 nm)/BPvTP (40 nm)/Liq(2 nm)/Al (1.00 nm), where HATCN is1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile NPD isN,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine, BisPCz is9,9′-diphenyl-9H,9′H-3,3′-bicarbazole, mCBT is3,3′-di(9H-carbazol-9-yl)-1,1′-biphenyl, BPyTP is2,7-di(2,2′-bipyridin-5-yl)triphenylene and Liq is 8-hydroxyquinolinelithium. FIG. 5D shows device operational lifetime.

Example 4

Synthesis of DFE-4

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 3-chloro-4-iodopyridine (1.2 eq). Then, BImPhen (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-4 in 31% yield.

Example 5

Synthesis of DFE-5

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 4-chloro-3-iodopyridine (1.2 eq). Then, BImPhen (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-5 in 29% yield.

Example 6

Synthesis of DFE-6

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 1,2-dibromobenzene (1.2 eq). Then, BImPhen (1 eq)and DMF (0.15 M) were added to the reaction mixture under the protectionof N₂. The reaction mixture was stirred for 10 min at room temperature,and then heated at 140° C. in a pre-heated oil bath for 24 h. Afterthat, the reaction mixture was cooled to room temperature, diluted withCH₂Cl₂, filtered through a short pad of Celite, and washed with CH₂Cl₂.The combined organic extracts were concentrated under reduced pressureand the resulting residue was purified by column chromatography onsilica gel to provide the product DFE-6 in 55% yield.

Example 7

Synthesis of DFE-6

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 4,5-dibromophthalonitrile (1.2 eq). Then, BImPhen(1 eq) and. DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-7 in 46% yield.

Example 8

Synthesis of DFE-8

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-bromo-3-chloropyridine (1.2 eq). Then. ImPhen (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DEE-8 in 24% yield.

Example 9

Synthesis of DFE-9

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2,3-dichloropyrazine (1.2 eq). Then, ImPhen (1 eq)and DMF (0.15 M) were added to the reaction mixture under the protectionof N₂. The reaction mixture was stirred for 10 min at room temperature,and then heated at 140° C. in a pre-heated oil bath for 24 h. Afterthat, the reaction mixture was cooled to room temperature, diluted withCH₂Cl₂, filtered through a short pad of Celite, and washed with CH₂Cl₂.The combined organic extracts were concentrated under reduced pressureand the resulting residue was purified by column chromatography onsilica gel to provide the product DFE-9 in 30% yield.

Example 10

Synthesis of DFE-10

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, ImPhen (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-10 in 34% yield.

Example 11

Synthesis of DFE-11

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 1,2-dibromobenzene (1.2 eq). Then, ImPhen (1 eq)and DMF (0.15 M) were added to the reaction mixture under the protectionof N₂. The reaction mixture was stirred for 10 min at room temperature,and then heated at 140° C. in a pre-heated oil bath for 24 h. Afterthat, the reaction mixture was cooled to room temperature, diluted withCH₂Cl₂, filtered through a short pad of Celite, and washed with CH₂Cl₂.The combined organic extracts were concentrated under reduced pressureand the resulting residue was purified by column chromatography onsilica gel to provide the product DFE-11 in 39% yield.

Example 12

Synthesis of DFE-6

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 4,5-dibromophthalonitrile (1.2 eq). Then, ImPhen(1 eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-12 in 37% yield.

Example 13

Synthesis of DFE-14

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 1,2-dibromobenzene (1.2 eq). Then, ImBT-1 (1 eq)and DMF (0.15 M) were added to the reaction mixture under the protectionof N₂. The reaction mixture was stirred for 10 min at room temperature,and then heated at 140° C. in a pre-heated oil bath for 24 h. Afterthat, the reaction mixture was cooled to room temperature, diluted withCH₂Cl₂, filtered through a short pad of Celite, and washed with CH₂Cl₂.The combined organic extracts were concentrated under reduced pressureand the resulting residue was purified by column chromatography onsilica gel to provide the product DFE-13 in 39% yield.

Example 14

Synthesis of DFE-8

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-bromo-3-chloropyridine (1.2 eq). Then. ImBT-1 (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-14 in 21% yield.

Example 15

Synthesis of DFE-15

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, ImBT-1 (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-15 in 34% yield.

Example 16

Synthesis of DFE-16

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and -chloro-3-iodopyridine (1.2 eq). Then, BImBT-1 (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-16 in 28% yield.

Example 17

Synthesis of DFE-17

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, BImBF-1.(1 eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-17 in 28% yield.

Example 18

Synthesis of DFE-18

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, BImPCz-1(1 eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-18 in 23% yield.

Example 19

Synthesis of DFE-19

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, BImBT-2 (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-19 in 21% yield.

Example 20

Synthesis of DFE-20

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, BImBT-2 (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-20 in 26% yield.

Example 21

Synthesis of DFE-21

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then. BImPCz-2(1 eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-21 in 23% yield.

Example 22

Synthesis of DFE-22

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, BImPAd-1(1 eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-22 in 19% yield.

Example 23

Synthesis of DFE-23

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, BImBT-3 (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-23 in 25% yield.

Example 24

Synthesis of DFE-24

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, BImBF-3 (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-24 in 20% yield.

Example 25

Synthesis of DFE-25

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and -chloro-3-iodopyridine (1.2 eq). Then, BImBF-3 (Ieq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-25 in 20?/yield.

Example 26

Synthesis of DFE-26

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, BImPAd-2(1 and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-26 in 18% yield.

Example 27

Synthesis of DFE-27

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, BImBT-4 (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-27 in 24% yield.

Example 28

Synthesis of DFE-28

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and -chloro-3-iodopyridine (1.2 eq). Then, BImBF-4 (Ieq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-28 in 21% yield.

Example 29

Synthesis of DFE-29

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, BImPCz-4(1 eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-29 in 27% yield.

Example 30

Synthesis of DFE-30

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 1,2-dibromobenzene (1.2 eq). Then, PBT-1 (1 eq)and DMF (0.15 M) were added to the reaction mixture under the protectionof N₂. The reaction mixture was stirred for 10 min at room temperature,and then heated at 140° C. in a pre-heated oil bath for 24 h. Afterthat, the reaction mixture was cooled to room temperature, diluted withCH₂Cl₂, filtered through a short pad of Celite, and washed with CH₂Cl₂.The combined organic extracts were concentrated under reduced pressureand the resulting residue was purified by column chromatography onsilica gel to provide the product DFE-30 in 43% yield.

Example 31

Synthesis of DFE-31

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-bromo-3-chloropyridine (1.2 eq). Then. PBT-1 (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-31 in 17% yield.

Example 32

Synthesis of DFE-32

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-chloro-3-iodopyridine (1.2 eq). Then, PBT-1 (1eq) and DMF (0.15 M) were added to the reaction mixture under theprotection of N₂. The reaction mixture was stirred for 10 min at roomtemperature, and then heated at 140° C. in a pre-heated oil bath for 24h. After that, the reaction mixture was cooled to room temperature,diluted with CH₂Cl₂, filtered through a short pad of Celite, and washedwith CH₂Cl₂. The combined organic extracts were concentrated underreduced pressure and the resulting residue was purified by columnchromatography on silica gel to provide the product DFE-32 in 21% yield.

Example 33

Synthesis of DFE-33

MoCl₅ (1.0 equiv) was added quickly to a solution of4,5-di(naphthalen-1-yl)phthalonitrile (1.00 equiv) in CH₂Cl₂ (0.05 M)under nitrogen. The mixture was stirred at room temperature for 24 h;then the other one equiv of MoCl₅ was added quickly to the mixtureagain. After being stirred for 24 h, the mixture was quenched bymethanol and stirred for another 1 h, filtered, and washed with CH₂Cl₂.The filtrate was concentrated, and the residue was purified throughcolumn chromatography on silica gel to afford the product DFE-33 in 41%yield.

Example 34

Synthesis of DFE-34

MoCl₅ (1.0 equiv) was added quickly to a solution of4,5-di(naphthalen-2-yl)phthalonitrile (1.00 equiv) in CH₂Cl₂ (0.05 M)under nitrogen. The mixture was stirred at room temperature for 24 h;then the other one equiv of MoCl₅ was added quickly to the mixtureagain. After being stirred for 24 h, the mixture was quenched bymethanol and stirred for another 1 h, filtered, and washed with CH₂Cl₂.The filtrate was concentrated, and the residue was purified throughcolumn chromatography on silica gel to afford the product DFE-33 in 37%yield.

Example 35

Synthesis of DFE-35

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2-bromo-3-chloropyridine (1.2 eq). Then,2-phenyl-1H-indole (1 eq) and DMF (0.15 M) were added to the reactionmixture under the protection of N₂. The reaction mixture was stirred for10 min at room temperature, and then heated at 140° C. in a pre-heatedoil bath for 24 h. After that, the reaction mixture was cooled to roomtemperature, diluted with CH₂Cl₂, filtered through a short pad ofCelite, and washed with CH₂Cl₂. The combined organic extracts wereconcentrated under reduced pressure and the resulting residue waspurified by column chromatography on silica gel to provide the productDFE-35 in 29% yield.

Example 36

Synthesis of DFE-36

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 2,3-dibromopyrazine (1.2 eq). Then,2-phenyl-1H-indole (1 eq) and DMF (0.15 M) were added to the reactionmixture wider the protection of N₂. The reaction mixture was stirred for10 min at room temperature, and then heated at 140° C. in a pre-heatedoil bath for 24 h. After that, the reaction mixture was cooled to roomtemperature, diluted with CH₂Cl₂, filtered through a short pad ofCelite, and washed with CH₂Cl₂. The combined organic extracts wereconcentrated under reduced pressure and the resulting residue waspurified by column chromatography on silica gel to provide the productDFE-36 in 25% yield.

Example 37

Synthesis of DFE-37

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and 5,6-dibromopyrazine-2,3-dicarbonitrile (1.2 eq).Then, 2-phenyl-1H-indole (1 eq) and DMF (0.15 M) were added to thereaction mixture under the protection of N₂. The reaction mixture wasstirred for 10 min at room temperature, and then heated at 140° C. in apre-heated oil bath for 24 h. After that, the reaction mixture wascooled to room temperature, diluted with CH₂Cl₂, filtered through ashort pad of Celite, and washed with CH₂Cl₂. The combined organicextracts were concentrated under reduced pressure and the resultingresidue was purified by column chromatography on silica gel to providethe product DFE-37 in 22% yield.

Example 38

Synthesis of DFE-38

To a flame-dried flask were added Pd(PPh₃)₄ (10 mol %), Xantphos (10 mol%), Cs₂CO₃ (3 eq) and -chloro-3-iodopyridine (1.2 eq). Then,2-phenyl-1H-indole (1 eq) and DMF (0.15 M) were added to the reactionmixture under the protection of N₂. The reaction mixture was stirred for10 min at room temperature, and then heated at 140° C. in a pre-heatedoil bath for 24 h. After that, the reaction mixture was cooled to roomtemperature, diluted with CH₂Cl₂, filtered through a short pad ofCelite, and washed with CH₂Cl₂. The combined organic extracts wereconcentrated under reduced pressure and the resulting residue waspurified by column chromatography on silica gel to provide the productDFE-38 in 25% yield.

Only a few implementations are described and illustrated. Variations,enhancements and improvements of the described implementations and otherimplementations can be made based on what is described and illustratedin this document.

What is claimed is:
 1. A compound represented by the formula:

wherein:

wherein: each R¹ independently represents hydrogen, deuterium, halogen,cyano, isonitrile, nitro, alkyl, haloalkyl, aralkyl, alkenyl, alkynyl,carbamoyl, carboxy, alkoxycarbonyl, amino, monoalkylamino,monoarylamino, dialkylamino, diarylamino, acylamino, ureido,alkoxycarbonylamino, aryloxycarbonylamino, hydrazino,alkylsulfonylamino, arylsulfonylamino, hydroxy, alkoxy, aryloxy,trialkylsilyl, trialkoxysilyl, triarylsilyl, phosphoramide, thiol,alkylthio, alkylsulfinyl, sulfamoyl, sulfonic acid, cycloalkyl,cycloalkenyl, heterocyclyl, aryl, or heteroaryl; and each R²independently represents hydrogen, deuterium, halogen, cyano,isonitrile, nitro, alkyl, haloalkyl, aralkyl, alkenyl, alkynyl,carbamoyl, carboxy, alkoxycarbonyl, amino, monoalkylamino,monoarylamino, dialkylamino, diarylamino, acylamino, ureido,alkoxycarbonylamino, aryloxycarbonylamino, hydrazino,alkylsulfonylamino, arylsulfonylamino, hydroxy, alkoxy, aryloxy,trialkylsilyl, trialkoxysilyl, triarylsilyl, phosphoramide, thiol,alkylthio, alkylsulfinyl, sulfamoyl, sulfonic acid, cycloalkyl,cycloalkenyl, heterocyclyl, aryl, or heteroaryl;

wherein: each R¹ independently represents hydrogen, deuterium, halogen,cyano, isonitrile, nitro, alkyl, haloalkyl, aralkyl, alkenyl, alkynyl,carbamoyl, carboxy, alkoxycarbonyl, amino, monoalkylamino,monoarylamino, dialkylamino, diarylamino, acylamino, ureido,alkoxycarbonylamino, aryloxycarbonylamino, hydrazino,alkylsulfonylamino, arylsulfonylamino, hydroxy, alkoxy, aryloxy,trialkylsilyl, trialkoxysilyl, triarylsilyl, phosphoramide, thiol,alkylthio, alkylsulfinyl, sulfamoyl, sulfonic acid, cycloalkyl,cycloalkenyl, heterocyclyl, or heteroaryl; and

wherein: each R¹ independently represents hydrogen, deuterium, halogen,cyano, isonitrile, nitro, alkyl, haloalkyl, aralkyl, alkenyl, alkynyl,carbamoyl, carboxy, alkoxycarbonyl, amino, monoalkylamino,monoarylamino, dialkylamino, diarylamino, acylamino, ureido,alkoxycarbonylamino, aryloxycarbonylamino, hydrazino,alkylsulfonylamino, arylsulfonylamino, hydroxy, alkoxy, aryloxy,trialkylsilyl, trialkoxysilyl, triarylsilyl, phosphoramide, thiol,alkylthio, alkylsulfinyl, sulfamoyl, sulfonic acid, cycloalkyl,cycloalkenyl, heterocyclyl, aryl, or heteroaryl; wherein the alkyl,haloalkyl, aralkyl, alkenyl, alkynyl, carbamoyl, alkoxycarbonyl, amino,monoalkylamino, monoarylamino, dialkylamino, diarylamino, acylamino,ureido, alkoxycarbonylamino, aryloxycarbonylamino, alkylsulfonylamino,arylsulfonylamino, alkoxy, aryloxy, trialkylsilyl, trialkoxysilyl,triarylsilyl, phosphoramide, alkylthio, sulfamoyl, cycloalkyl,cycloalkenyl, heterocyclyl, aryl, and heteroaryl of each R¹ and R² isoptionally and independently substituted with one or more substituentsindependently selected from the group consisting of deuterium, halogen,cyano, isonitrile, nitro, alkyl, haloalkyl, aralkyl, alkenyl, alkynyl,carbamoyl, carboxy, alkoxycarbonyl, amino, monoalkylamino,monoarylamino, dialkylamino, diarylamino, acylamino, ureido,alkoxycarbonylamino, aryloxycarbonylamino, hydrazino,alkylsulfonylamino, arylsulfonylamino, hydroxy, alkoxy, aryloxy,trialkylsilyl, trialkoxysilyl, triarylsilyl, phosphoramide, thiol,alkylthio, alkylsulfinyl, sulfamoyl, sulfonic acid, cycloalkyl,cycloalkenyl, heterocyclyl, aryl, and heteroaryl; with the proviso thatthe compound is not:


2. The compound of claim 1, wherein the compound is selected from thegroup consisting of:


3. A light emitting diode comprising the compound of claim
 1. 4. A lightemitting device comprising the light emitting diode of claim
 3. 5. Acompound represented by the formula:

wherein:

X² represents O or S; each R¹ independently represents hydrogen,deuterium, halogen, cyano, isonitrile, nitro, alkyl, haloalkyl, aralkyl,alkenyl, alkynyl, carbamoyl, carboxy, alkoxycarbonyl, amino,monoalkylamino, monoarylamino, dialkylamino, diarylamino, acylamino,ureido, alkoxycarbonylamino, aryloxycarbonylamino, hydrazino,alkylsulfonylamino, arylsulfonylamino, hydroxy, alkoxy, aryloxy,trialkylsilyl, trialkoxysilyl, triarylsilyl, phosphoramide, thiol,alkylthio, alkylsulfinyl, sulfamoyl, sulfonic acid, cycloalkyl,cycloalkenyl, heterocyclyl, aryl, or heteroaryl; and each R²independently represents hydrogen, deuterium, halogen, cyano,isonitrile, nitro, alkyl, haloalkyl, aralkyl, alkenyl, alkynyl,carbamoyl, carboxy, alkoxycarbonyl, amino, monoalkylamino,monoarylamino, dialkylamino, diarylamino, acylamino, ureido,alkoxycarbonylamino, aryloxycarbonylamino, hydrazino,alkylsulfonylamino, arylsulfonylamino, hydroxy, alkoxy, aryloxy,trialkylsilyl, trialkoxysilyl, triarylsilyl, phosphoramide, thiol,alkylthio, alkylsulfinyl, sulfamoyl, sulfonic acid, cycloalkyl,cycloalkenyl, heterocyclyl, aryl, or heteroaryl; wherein the alkyl,haloalkyl, aralkyl, alkenyl, alkynyl, carbamoyl, alkoxycarbonyl, amino,monoalkylamino, monoarylamino, dialkylamino, diarylamino, acylamino,ureido, alkoxycarbonylamino, aryloxycarbonylamino, alkylsulfonylamino,arylsulfonylamino, alkoxy, aryloxy, trialkylsilyl, trialkoxysilyl,triarylsilyl, phosphoramide, alkylthio, sulfamoyl, cycloalkyl,cycloalkenyl, heterocyclyl, aryl, and heteroaryl of each IV and IV isoptionally and independently substituted with one or more substituentsindependently selected from the group consisting of deuterium, halogen,cyano, isonitrile, nitro, alkyl, haloalkyl, aralkyl, alkenyl, alkynyl,carbamoyl, carboxy, alkoxycarbonyl, amino, monoalkylamino,monoarylamino, dialkylamino, diarylamino, acylamino, ureido,alkoxycarbonylamino, aryloxycarbonylamino, hydrazino,alkylsulfonylamino, arylsulfonylamino, hydroxy, alkoxy, aryloxy,trialkylsilyl, trialkoxysilyl, triarylsilyl, phosphoramide, thiol,alkylthio, alkylsulfinyl, sulfamoyl, sulfonic acid, cycloalkyl,cycloalkenyl, heterocyclyl, aryl, and heteroaryl.
 6. The compound ofclaim 5, wherein the compound is selected from the group consisting of:


7. A light emitting diode comprising the compound of claim
 5. 8. A lightemitting device comprising the light emitting diode of claim 7.